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Formation and Dissociation Kinetics of Zinc(II) Complexes of Tetraaza-Crown-Alkanoic Acids (Zinc(Ⅱ) Tetraaza-Crown-Allkanoic Acids 착물의 형성 및 해리 반응속도론)

  • Choi, Ki Young;Kim, Dong Won;Kim, Chang Suk;Park, Byung Bin;Choi, Suk Nam;Hong, Choon Pyo;Ryu, Hae Il
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.403-409
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    • 2000
  • The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

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Identification and prevalence of trematode(Gen Azygia) and nematode(Gen Pingus) in Ophicephalus argus (가물치의 위장내 기생하는 흡충(Azygia속) 및 선충(Pingus속)의 동정과 감염상황)

  • Moon, Moo-hong;Lee, Eun-woo
    • Korean Journal of Veterinary Research
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    • v.38 no.1
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    • pp.147-159
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    • 1998
  • A survey of the internal parasites in 115 fishes of Ophicephalus argus was carried out in Kyungpook province during the period from January 1995 to November 1997. A species of trematode from the stomach and a species of nematode from the caeca of the fishes was discovered respectively. The trematode was identified as Azygia hwangtsinyi (Tsin, 1993) and the nematode as Pingus sinensis ($Hs\ddot{u}$, 1993). The fluke was pressed at thick of 0.1mm~0.2mm between slide glasses and fixed in 70% ethyl alcohol solution. The fluke was washed with tap water after fixation and stained with hematoxylin-carmin and mounted in balsam through routine methods. The nematode was fixed in 5% formalin solution and mounted with lactophnol or glycerine jelly. Morphology : Arygia hwantsinyi ; The fluke is elongate body with approximately parallel margins and rounded extremities in pressed preparations(Fig 1). The cuticle is unarmed. The oral sucker is ventro-subterminal in position. The ventral sucker is slightly smaller than oral sucker and positioned at 14.2% of body length from the oral sucker. The cirrus sac and genital pore is in mid-ventral line, slightly anterior to the ventral sucker. The oral sucker is succeeded by a well developed muscular pharynx. It is succeeded by a short inverted Y-shaped oesophagus. The inner wall of oesophagus is consisted of many fine folded membrane. The fine tubes of esophagus pass into the intestinal heads which are distended and presented a marked borderline between the fine tube and intestinal heads. The Intestinal heads start at level of pharynx and pass caudad in a zigzag course to end quite near caudal margin. The uterine coils occupy the intercecal area between the level of the cephalic margin of the ovary and about the level of the ventral sucker. The uterus is filled with many eggs. The testes are round or oval and placed one behind the other generally a little diagonally. The posterior testis is placed at level of 75.1% of body length. The ovary is oval, placed ahead the anterior testis. The shell gland not discernible outline is contacted with ovary ahead it. The vitelline glands are consisted of small oval vesicles. The vesicles occupy extracecal regions and between a little posterior of the ventral sucker and near caudal margin. Pingus sinensis : Female ; The cuticle is smooth and the cervical alae are well developed. The mouth opening is small, triangular, and without lips. The anterior end bears four sub-medial papillae. The oesophagus is divided into a muscular and glandular portion. The nerve ring is situated just at the junction of the muscular and glandular portions of the oesophagus. The vulva which has a prominent flap, is placed behind the middle of the body about one-third of the length of the worm from the posterior extremity. The vagina is strongly muscularised and after running anteriorly about $68{\mu}$, divides itself into two broad uterine tubes with an anterior and a posterior one. There are a few eggs in the uterine tubes. The tail is slender, straight and pointed. The ovary extends almost to the posterior extremity. Male : Male is smaller than female. The tail is pointed, curved and carrying well-developed caudal alae. A prominent muscular precloacal sucker is characteristic. The spicules are equal and short. There are four pairs of pedunculated pre-anal papillae, of which the most anterior pair are situated just at the level anterior to the muscular sucker. Two pairs of pedunculated papillae are present before the anus. There are five pairs of post-anal papillae of which the most anterior pair and the second counted from the posterior end are ventral and more marked than the ones which are situated laterally.

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The Anti-angiogenic Potential of a Phellodendron amurense Hot Water Extract in Vitro and ex Vivo (in Vitro와 ex vivo에서 황백 온수추출물의 신생혈관 억제효과)

  • Kim, Eok-Cheon;Kim, Seo Ho;Bae, Kiho;Kim, Han Sung;Gelinsky, Michael;Kim, Tack-Joong
    • Journal of Life Science
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    • v.25 no.6
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    • pp.693-702
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    • 2015
  • Blocking new blood-vessel formation (angiogenesis) is now recognized as a useful approach to the therapeutic treatment of many solid tumors. The best validated approach to date is to target the vascular endothelial growth-factor (VEGF) pathway, a key regulator of angiogenesis. Many natural products and extracts that contain a variety of chemopreventive compounds have been shown to suppress the development of malignancies through their anti-angiogenic properties. Phellodendron amurense, which is widely used in Korean traditional medicine, has been shown to possess antitumor, antimicrobial, and anti-inflammatory properties, among others. The present study investigated the effects of P. amurense hot-water extract (PAHWE) on angiogenesis, a key process in tumor growth, invasion, and metastasis. To investigate PAHWE’s anti-angiogenic properties, this study’s authors performed an analysis of angiogenesis and endothelial-cell proliferation, migration, invasion, and tube formation, as well as zymogram assays and the rat aortic ring-sprouting assay. PAHWE inhibited cell growth, mobility, and vessel formation in response to VEGF in vitro and ex vivo. Furthermore, it reduced VEGF-induced intracellular signaling events, such as the activation of matrix metalloproteinases (MMPs) -2 and -9. These results indicate that PAHWE’s anti-angiogenic properties might lead to the development of potential drugs for treating angiogenesis-associated diseases such as cancer.

Isolation and Identification of a Photosensitizer from Pueraria thunbergiana Leaves that Induces Apoptosis in SK-HEP-1 Cells (P. thunbergiana 잎으로부터 SK-HEP-1세포에 대한 apoptosis를 유도하는 광과민성물질의 분리 및 구조동정)

  • Lee, Jun Young;Kim, Mi Kyeong;Ha, Jun Young;Kim, Yong Gyun;Hong, Chang Oh;Kim, So Young;Kim, Chung-Hwan;Kim, Keun Ki
    • Journal of Life Science
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    • v.24 no.3
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    • pp.242-251
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    • 2014
  • The objective of this study was to isolate a photosensitizer from Pueraria thunbergiana leaves that induces apoptosis in SK-HEP-1 cells. Column chromatography and thin layer chromatography were used to isolate active compounds from extracts of P. thunbergiana leaves. The structures of the isolated compounds were determined by 1D-NMR, 2D-NMR, and FAB-mass spectroscopy. A substance, named M4-3, was purified from the leaves of P. thunbergiana using various chromatography methods, and the absorbance of the substance was measured. The absorbance was highest at 410 nm, suggesting that the M4-3 substance was a different compound from chlorophyll a and b, which absorb at 410, 502, 533, and 607 nm. Further analyses revealed that the M4-3 compound was a $13^2$-hydoxy pheophorbide, a methyl ester with a molecular weight of 662. M4-3 was identified as a derivative compound of pheophorbide, with a structure that magnesium comes away from the porphyrin ring. The results of the analysis of the cytotoxicity of the M4-3 substance against the SK-HEP-1 cells revealed that it inhibited rates of cell growth by 40% and 80% at a concentration of 0.04 ${\mu}M$ and 0.08 ${\mu}M$, respectively. The M4-3 compound was found to be a photosensitizer for cytotoxicity because it was appeared only in light condition as examining activity in different irradiation conditions (light condition and nonlight condition) under the same concentration. Analysis of morphological changes in the cells following cell death induced by exposure to the M4-3 substance reveled representative phenomena of apoptosis (nuclear condensation, vesicle formation, and fragmentation of DNA). The induction of apoptosis was attributed to the compound's photodynamic activity.

Lessons from Cross-Scale Studies of Water and Carbon Cycles in the Gwangneung Forest Catchment in a Complex Landscape of Monsoon Korea (몬순기후와 복잡지형의 특성을 갖는 광릉 산림유역의 물과 탄소순환에 대한 교차규모 연구로부터의 교훈)

  • Lee, Dong-Ho;Kim, Joon;Kim, Su-Jin;Moon, Sang-Ki;Lee, Jae-Seok;Lim, Jong-Hwan;Son, Yow-Han;Kang, Sin-Kyu;Kim, Sang-Hyun;Kim, Kyong-Ha;Woo, Nam-Chil;Lee, Bu-Yong;Kim, Sung
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.9 no.2
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    • pp.149-160
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    • 2007
  • KoFlux Gwangneung Supersite comprises complex topography and diverse vegetation types (and structures), which necessitate complementary multi-disciplinary measurements to understand energy and matter exchange. Here, we report the results of this ongoing research with special focuses on carbon/water budgets in Gwangneung forest, implications of inter-dependency between water and carbon cycles, and the importance of hydrology in carbon cycling under monsoon climate. Comprehensive biometric and chamber measurements indicated the mean annual net ecosystem productivity (NEP) of this forest to be ${\sim}2.6\;t\;C\;ha^{-1}y^{-1}$. In conjunction with the tower flux measurement, the preliminary carbon budget suggests the Gwangneung forest to be an important sink for atmospheric $CO_2$. The catchment scale water budget indicated that $30\sim40%$ of annual precipitation was apportioned to evapotranspiration (ET). The growing season average of the water use efficiency (WUE), determined from leaf carbon isotope ratios of representative tree species, was about $12{\mu}mol\;CO_2/mmol\;H_2O$ with noticeable seasonal variations. Such information on ET and WUE can be used to constrain the catchment scale carbon uptake. Inter-annual variations in tree ring growth and soil respiration rates correlated with the magnitude and the pattern of precipitation during the growing season, which requires further investigation of the effect of a monsoon climate on the catchment carbon cycle. Additionally, we examine whether structural and functional units exist in this catchment by characterizing the spatial heterogeneity of the study site, which will provide the linkage between different spatial and temporal scale measurements.

Understanding the protox inhibition activity of novel 1-(5-methyl-3-phenylisoxazolin-5-yl)methoxy-2-chloro-4-fluorobenzene derivatives using comparative molecular field analysis (CoMFA) methodology (비교 분자장 분석 (CoMFA) 방법에 따른 1-(5-methyl-3-phenylisoxazolin-5-yl)methoxy-2-chloro-4-fluoro-benzene 유도체들의 Protox 저해 활성에 관한 이해)

  • Sung, Nack-Do;Song, Jong-Hwan;Yang, Sook-Young;Park, Kyeng-Yong
    • The Korean Journal of Pesticide Science
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    • v.8 no.3
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    • pp.151-161
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    • 2004
  • Three dimensional quantitative structure-activity relationships (3D-QSAR) studies for the protox inhibition activities against root and shoot of rice plant (Orysa sativa L.) and barnyardgrass (Echinochloa crus-galli) by a series of new A=3,4,5,6-tetrahydrophthalimino, B=3-chloro-4,5,6,7-tetrahydro-2H-indazolyl and C=3,4-dimethylmaleimino group, and R-group substituted on the phenyl ring in 1-(5-methyl-3-phenylisoxazolin-5-yl)methoxy-2chloro-4-fluorobenzene derivatives were performed using comparative molecular field analyses (CoMFA) methodology with Gasteiger-Huckel charge. Four CoMFA models for the protox inhibition activities against root and shoot of the two plants were generated using 46 molecules as training set and the predictive ability of the each models was evaluated against a test set of 8 molecules. And the statistical results of these models with combination (SIH) of standard field, indicator field and H-bond field showed the best predictability of the protox inhibition activities based on the cross-validated value $r^2_{cv.}$ $(q^2=0.635\sim0.924)$, conventional coefficient $(r^2_{ncv.}=0.928\sim0.977)$ and PRESS value $(0.091\sim0.156)$, respectively. The activities exhibited a strong correlation with steric $(74.3\sim87.4%)$, electrostatic $(10.10\sim18.5%)$ and hydrophobic $(1.10\sim8.30%)$ factors of the molecules. The steric feature of molecule may be an important factor for the activities. We founded that an novel selective and higher protox inhibitors between the two plants may be designed by modification of X-subsitutents for barnyardgrass based upon the results obtained from CoMFA analyses.

Effect of Phenolic Mediators and Humic Acid on the Removal of 1-Indanone Using Manganese Oxide (망간산화물(Birnessite)을 이용한 1- Indanone 제거 시 페놀계 반응매개체와 휴믹산(HA) 영향 평가)

  • Choi, Chan-Kyu;Eom, Won-Suk;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.7
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    • pp.445-453
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    • 2012
  • An investigation for removal of 1-indanone (1-ID), which were commonly produced from the biological and/or chemical treatment and natural weathering of the PAHs-contaminated soils, via oxidative transformation mediated by birnessite in the presence of various phenolic mediators is described. This study also examines the potential effect of the natural occurring substance humic acid (HA) on the oxidative transformation. The experiment was carried out in aqueous phase as a batch test (10 mg/L 1-ID, 0.3 mM phenolic mediators, $1.0g/L\;{\delta}-MnO_2$, at pH 5). All of the 11 tested phenoilic mediators belong to the group of natural occurring phenols and are widely used as model constituents of humic substances. From the results of HPLC analysis, it is demonstrated that 1-ID was not reactive to birnessite itself, but it can be effectively removed in birnessite-mediated cross coupling reactions in the presence of the phenolic mediators. The percent removals of 1-ID after 2 day incubation were ranged from 9.2 to 71.2% depending on the phenolic mediators applied. The initial rate constant ($K_{int}$, $hr^{-1}$) values for the 1-ID removals obtained from the pseudo-first-order kinetic plots also widely ranged from 0.18 to 15.0. Results of the correlative analysis between the removal efficiencies and structural characteristics of phenolic mediators indicate that the transformation of the 1-ID was considerably enhanced by the addition of electron-donating substituents (e.g., -OH, $-OCH_3$) at the benzne ring, and much less enhanced by the addition of electron-withdrawing substituents (e.g., -COOH, -CHO). The presence of HA showed that removal efficiencies of 1-ID in the birnessite-phenolic mediator systems decreased with increasing HA concentrations. However at low concentration of HA (< 2 mg/L), it caused some enhancement in the removals of 1-ID as compared to the control.

Synthesis of Fully Dehydrated Partially Cs+-exchanged Zeolite Y (FAU, Si/Al = 1.56), |Cs45Na30|[Si117Al75O384]-FAU and Its Single-crystal Structure

  • Seo, Sung-Man;Kim, Ghyung-Hwa;Lee, Seok-Hee;Bae, Jun-Seok;Lim, Woo-Taik
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1285-1292
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    • 2009
  • Large single crystals of zeolite, |$Na_{75}$|[$Si_{117}Al_{75}O_{384}$]-FAU (Na-Y, Si/Al = 1.56), were synthesized from gels with composition of 3.58Si$O_2$ : 2.08NaAl$O_2$ : 7.59NaOH : 455$H_2$O : 5.06TEA : 2.23TCl. One of these, a colorless single-crystal was ion exchanged by allowing aqueous 0.02 M CsOH to flow past the crystal at 293 K for 3 days, followed by dehydration at 673 K and 1 ${\times}\;10^{-6}$ Torr for 2 days. The crystal structure of fully dehydrated partially $Cs^+$-exchanged zeolite Y, |$Cs_{45}Na_{30}$|[$Si_{117}Al_{75}O_{384}$]-FAU per unit cell (a = 24.9080(10) $\AA$) was determined by single-crystal X-ray diffraction technique in the cubic space group Fd $\overline{3}$ m at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 877 reflections with $F_o\;>\;4{\sigma}(F_o))\;R_1$ = 0.0966 (Based on F) and $R_2\;=\;0.2641\;(Based\;on\;F^2$). About forty-five $Cs^+$ ions per unit cell are found at six different crystallographic sites. The 2 $Cs^+$ ions occupied at site I, at the centers of double 6-ring (D6Rs, Cs-O = 2.774(10) $\AA$ and O-Cs-O = 88.9(3) and 91.1(3)$^o$). Two $Cs^+$ ions are found at site I’ in the sodalite cavity; the $Cs^+$ ions were recessed 2.05 $\AA$ into the sodalite cavity from their 3-oxygen plane (Cs-O = 3.05(3) $\AA$ and O-Cs-O = 77.4(13)$^o$). Site-II’ positions (opposite single 6-rings in the sodalite cage) are occupied by 7 $Cs^+$ ions, each of which extends 2.04 $\AA$ into the sodalite cage from its 3-oxygen plane (Cs-O = 3.067(11) $\AA$ and O-Cs-O = 80.1(3)$^o$). The 26 $Cs^+$ ions are nearly three-quarters filled at site II in the supercage, being recessed 2.34 $\AA$ into the supercage (Cs-O = 3.273(8) $\AA$ and O-Cs-O = 74.3(3)$^o$). The 4 $Cs^+$ ions are found at site III deep in the supercage (Cs-O = 3.321(19) and 3.08(3) $\AA$), and 4 $Cs^+$ ions at another site III’ (Cs-O = 2.87(4) and 3.38(4) $\AA$). About 30 $Na^+$ ions per unit cell are found at one crystallographic site; The $Na^+$ ions are located at site I’ in the sodalite cavity opposite double 6-rings (Na-O = 2.578(11) $\AA$ and O-Na-O = 97.8(4)$^o$).

List-event Data Resampling for Quantitative Improvement of PET Image (PET 영상의 정량적 개선을 위한 리스트-이벤트 데이터 재추출)

  • Woo, Sang-Keun;Ju, Jung Woo;Kim, Ji Min;Kang, Joo Hyun;Lim, Sang Moo;Kim, Kyeong Min
    • Progress in Medical Physics
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    • v.23 no.4
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    • pp.309-316
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    • 2012
  • Multimodal-imaging technique has been rapidly developed for improvement of diagnosis and evaluation of therapeutic effects. In despite of integrated hardware, registration accuracy was decreased due to a discrepancy between multimodal image and insufficiency of count in accordance with different acquisition method of each modality. The purpose of this study was to improve the PET image by event data resampling through analysis of data format, noise and statistical properties of small animal PET list data. Inveon PET listmode data was acquired as static data for 10 min after 60 min of 37 MBq/0.1 ml $^{18}F$-FDG injection via tail vein. Listmode data format was consist of packet containing 48 bit in which divided 8 bit header and 40 bit payload space. Realigned sinogram was generated from resampled event data of original listmode by using adjustment of LOR location, simple event magnification and nonparametric bootstrap. Sinogram was reconstructed for imaging using OSEM 2D algorithm with 16 subset and 4 iterations. Prompt coincidence was 13,940,707 count measured from PET data header and 13,936,687 count measured from analysis of list-event data. In simple event magnification of PET data, maximum was improved from 1.336 to 1.743, but noise was also increased. Resampling efficiency of PET data was assessed from de-noised and improved image by shift operation of payload value of sequential packet. Bootstrap resampling technique provides the PET image which noise and statistical properties was improved. List-event data resampling method would be aid to improve registration accuracy and early diagnosis efficiency.

Crystal Structure of Dehydrated Partially Cobalt(II)-Exchanged Zeolite X, $Co_{41}Na_{10}-X$ (부분적으로 $Co^{2+}$ 이온으로 치환된 제올라이트 X, $Co_{41}Na_{10}-X$를 탈수한 결정구조)

  • Jang, Se-Bok;Jeong, Mi-Suk;Han, Young-Wook;Kim, Yang
    • Korean Journal of Crystallography
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    • v.6 no.2
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    • pp.125-133
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    • 1995
  • The crystal structure of dehydrated, partially Co(II)-exchanged zeolite X, stoichiometry Co2+Na+-X (Co41+Na10Si100Al92O384) per unit cell, has been determined from three-dimensional X-ray diffraction data gathered by counter methods. The structure was solved and refined in the cubic space group Fd3:α=24.544(1)Å at 21(1)℃. The crystal was prepared by ion exchange in a flowing stream using a solution 0.025 M each in Co(NO3)2 and Co(O2CCH3)2. The crystal was then dehydrated at 380℃ and 2×10-6 Torr for two days. The structure was refined to the final error indices, R1=0.059 and R2=0.046 with 211 reflections for which I > 3σ(I). Co2+ ions and Na+ ions are located at the four different crystallographic sites. Co2+ ions are located at two different sites of high occupancies. Sixteen Co2+ ions are located at the center of the double six-ring (site I; Co-O = 2.21(1)Å, O-Co-O = 90.0(4)°) and twenty-five Co2+ ions are located at site II in the supercage. Twenty-five Co2+ ions are recessed 0.09Å into the supercage from its three oxygen plane (Co-O = 2.05(1)Å, O-Co-O = 119.8(7)°). Na+ ions are located at two different sites of occupandies. Seven Na+ ions are located at site II in the supercage (Na-O = 2.29(1)Å, O-Na-O = 102(1)°). Three Na+ ions are statistically distribyted over site III, a 48-fold equipoint in the supercages on twofold axes (Na-O = 2.59(10)Å, O-Na-O = 69.0(3)°). Seven Na+ ions are recessed 1.02Å into the supercage from the three oxygen plane. It appears that Co2+ ions prefer sites I and II in order, and that Na+ ions occupy the remaining sites, II and III.

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